Chloroprene polymer processing

ABSTRACT

IMPROVED COMPOUNDING AND PROCESSING OF CHLOROPRENE POLYMERS EMPLOYING A DISPERSIBLE FORM OF MGO AND PENTAERYTHRITOL AND ESTERS THEREOF.

United States Patent 3,810,856 CHLOROPRENE POLYMER PROCESSING Albert J. Dalhuisen, Sunnyvale, and William H. Deis,

Belmont, Califi, assignors to Merck & Co., Inc., Rahway, NJ.

No Drawing. Continuation-impart of abandoned application Ser. No. 87,318, Nov. 5, 1970. This application Nov. 9, 1972, Ser. No. 305,043

Int. Cl. C08d 9/14 US. Cl. 260-23.7 M 42 Claims ABSTRACT OF THE DISCLOSURE Improved compounding and processing of chloroprene polymers employing a dispersible form of MgO' and pentaerythritol and esters thereof.

This application is a coutinuation-in-part of United States patent application Ser. No. 87,318, filed Nov. 5, 1970, now abandoned.

This invention relates to improvements in the processing of rubber materials. More particularly this invention is concerned with an improved form of magnesium oxide dispersion for use in regulating the scorch and cure rate of neoprene rubber formulations. In addition, the MgO material of this invention results in the production of neoprene vulcanizates of excellent quality.

Neoprene is the generic term applied to the group of synthetic elastomers based on the polymers of chloroprene (2-chloro-l,3-butadiene). The group of general purpose neoprene formulations includes broadly two classes, the sulfur-modified (for example, Type G neoprene) and the nonsulfur-modified (for example, Type W neoprene). It should be understood that this invention is applicable to all types of chloroprene polymers made by polymerization, for example, in the presence of mercaptans or other modifying (chain transfer) agents such as the dialkyl xanthogen disulfides, or in the presence of sulfur, followed by plasticizing treatment, or by very limited polymerization without agents followed by removal of the unchanged chloroprene monomer. All these processes are fully described in the prior art. See for example U.S. Pats. 1,950,436; 2,227,517; 2,234,215; and 2,567,117. Neoprene GNA is an example of a G type of neprene. This particular neoprene is described and its method of manufacture is given at pages 769-771, Synthetic Rubber, edited by G. S. Whitby [John Wiley and Sons Inc. (1954)].

The polymers of chloroprene used include both polychloroprene itself and blends using a chloroprene polymer. Likewise, materials used with the chloroprene polymers as antioxidants, plasticizers, curing agents, accelerators, retarders, reinforcing agents, pigments and extenders are well known, as are the quantites which should be used under various circumstances. This prior art is applicable in the present invention.

The use of MgO in the processing of neoprene compounds is well-known. The mechanism by which MgO benefits the vulcanization process is not clearly understood, but the influence it exerts has been briefly described in Whitby Synthetic Rubber (1954), pages 775-776 (John Wiley) as providing a balance between processing safety and cure rate when the Mgo is combined with other oxides such as zinc oxide. The use of zinc oxide as the sole curing agent produces both a fast cure and a uniform state of cure on extended vulcanization; i.e., such stocks are fiat curing. The limitations of such compounds include a pronounced tendency to be scorchy, or result in a premature curing of the system. In addition, there results a leveling off of cure at a relatively low point. The use of magnesia as the sole curing agent produces 3,810,856 Patented May 14, 1974 lCC Neoprene compounds which are very slow curing and are safe processing, but in which curing activity tends to persist. In addition, magnesia improves vulcanizate againg properties, presumably by serving as acceptors for the minute amounts of hydrogen chloride which are released from the neoprene during processing curing and vulcanizate aging. In combination, zinc oxide and magnesia supplement each other to produce well-balanced stocks, the properties of which can be varied, frequently to advantage, by adjustment in the ratio of one oxide to the other.

It is the purpose of this invention to provide a synergistic mixture of highly reactive MgO and pentaerythritol and esters thereof for neoprene processing. The synergistic mixture of MgO and pentaerythritol 0r esters thereof and mixtures thereof of this invention, when employed in the processing of neoprene, result in improved Mooney Scorch Protection (original and after aging of the unvulcanized compound), and provide improved processing and storage safety of unvulcanized neoprene. Furthermore, the synergistic mixture has no adverse effect on the vulcanizate properties of neoprene. This results in less scrap and allows more latitude and flexibility in the processing and storage of the unvulcanized neoprene. This highly active, readily dispersible MgO and pentaerythritol formulation is composed of magnesium oxide and pentaerythritol or esters thereof or mixtures of the alcohol and esters thereof with a dispersing medium consisting of (a) at least one rubber plasticizer or (b) at least one surface active agent or (c) a mixture of at least one rubber plasticizer with at least one surface active agent.

MgO is currently employed in both powder and specitied dispersed form for use in neoprene processing. However, the pentaerythritol containing MgO dispersions of the invention result in the preparation of products with improved performance regarding Mooney Scorch Protection (original and after aging) when compared With the MgO preparations that are employed at this time in the rubber industry. The MgO dispersions of this invention may be utilized in either the liquid or solid state in the processing of neoprene. For example, the dispersions may be supplied to the neoprene manufacturer in the form of a paste, bar, stick, block or pellet, etc. in order that the dispersions may be conveniently utilized in the processing of neoprene. The particular form of the MgO dispersion involves a matter of choice and may be prepared using conventional procedures well known to the art.

It is well known in the industry that MgO, upon exposure to atmospheric moisture and carbon dioxide, is rapidly converted to the carbonate or hydroxide. However, neither magnesium carbonate nor magnesium hydroxide are effective in neoprene vulcanization in the manner in which MgO is effective. Accordingly, care must be continuously exercised to insure that the MgO preparation destined for use in neoprene processing does not experience a loss in activity. Another advantage of the dispersions of the invention relates to its ability to maintain the activity of the MgO over considerable periods of storage without employing the precautions normally confronting the industry.

This invention contemplates utilizing the neoprene grades of MgO which are precipitated and calcined after precipitation. In addition to these light calcined, highly surface active forms of MgO, less active types of MgO may also be employed in the practice of this invention. Included within this class of less active MgO materials are heavy calcined types of MgO.

The amount of pentaerythritol or esters thereof including mixtures thereof to be employed in the practice of this invention is not critical and may vary between about 2 and parts by weight of pentaerythritol or esters thereof per hundred parts of MgO. The preferred range may vary from about to 25 parts per hundred parts of MgO. The dispersion medium may consist of one of the following: (1) at least one rubber plasticizer; (2) at least one surface active agent; (3) a combination of at least one rubber plasticizer and at least one surface active agent. The amount of dispersing medium is not critical and may vary by weight from about 5 to 200 parts of medium per hundred parts by weight of MgO. When the dispersing medium consists of a mixture of rubber plasticizer and surface active agent the amount of plasticizer and surface active agent may vary within the range of 1% through 99% with relation to the other. In other words, to form an effective dispersing medium one may utilize a mixture of plasticizer and surface active agent wherein the mixture may be predominately rubber plasticizer or predominately surface active agent and all combinations included within such values.

The amount of MgO-pentaerythritol-dispersing medium to be employed in the processing of neoprene will usually vary from about 2 to 16 parts by weight per hundred parts of rubber. This will include systems where the synergistic mixture of MgO and pentaerythritol or esters thereof is used as a processing material both with and without the presence of other metallic oxides. For most applications, the recommended level is 4 phr.

The particular grade of pentaerythritol is not critical and any commercial source of pentaerythritol may be employed in the practice of the invention. For example the pure compound per se as well as a technical grade of pentaerythritol such as Hercules PE-200 having the following specifications is effective in the practice of the invention:

Monopentaerythritol content, percent 88:2 Hydroxyl content, percent 48:1 Ash (as Na SO percent 0.01 max. Total solids, percent 99.5 min. Color, ASTM Pt-Co 35 max. Fineness:

Retained on ZOO-mesh, percent Nil Retained on 325-mesh, percent 1.0 max.

The partial esters of pentaerythritol that are employed in the practice of the invention consist of mono-, diand tri-esters of pentaerythritol and carboxylic acids.

The acids from which the esters are derived include:

(a) Aliphatic monoand di-carboxylic acids containing from about 1 carbon atom per acid molecule (formic acid) to 18 carbon atoms (stearic acid).

The acids include saturated (acetic, heptanoic and lauric acids) and unsaturated acids (acrylic, sorbic and oleic acids).

The acids include saturated hydroxy acids (glycoxylic acid) and unsaturated hydroxy acids (ricinoleic acid).

The acids include oxo-acids (glycoxylic and acetoacetic acid).

The acids include saturated di-carboxylic acids (adipic and azelaic acid) and unsaturated di-carboxylic acids (maleic acid).

(b) The following aromatic acids are included: benzoic and phthalic acid.

Representative examples of esters which can be used in this invention are the mono-, diand tri-esters of pentaerythritol and the following carboxylic acids:

Formic Heptanoic Acetic Pivalic Acrylic Nonanoic Glycoxylic Azelaic Acetoacetic Glycolic Maleic Benzoic Adipic Phthalic Methacrylic The acids which find particular preference in the practice of the invention are fatty acids which contain from about 12-18 carbon atoms and include the following:

Oleic Lauric Stearic Palmitic Ricinoleic Linoleic Representative examples of specific pentaerythritol esters are as follows:

Pentaerythritol monostearate Pentaerythritol distearate Pentaerythritol tristearate Pentaerythritol monooleate Pentaerythritol dioleate Pentaerythritol trioleate Pentaerythritol monoricinoleate Pentaerythritol diricinoleate Pentaerythritol triricinoleate Pentaerythritol monopalmitate Pentaerythritol dipalmitate Pentaerythritol tripalmitate Pentaerythritol monolauratc Pentaerythritol dilaurate Pentaerythritol trilaurate Pentaerythritol monolinoleate Pentaerythritol dilinoleate Pentaerythritol monoricinoleate of which the following are of particular interest:

Pentaerythritol monostearate Pentaerythritol distearate Pentaerythritol tristearate Pentaerythritol monooleate Pentaerythritol dioleate Pentaerythritol monoricinoleate The particular rubber plasticizer that may be employed in the practice of this invention is not critical and includes those plasticizers that are well known and conventionally employed for this purpose by the skilled artisans of the rubber art. In this regard see Morton, Introduction to Rubber Technology, pages 151-171. Reinhold Publ. Comp. (1964); Murray and Thompson, The Neoprenes, pages 39-41, DuPont (1963); the plasticizers disclosed therein being incorporated by reference. Included among this class are:

Petroleum oils, such as parafiinic, naphthenic, and aromatic. Resin, waxes, and asphalt derived from petroleum oil are also encompassed within this class. For example, fully refined parafiin waxes may be employed in the practice of the invention. Fully refined paraffin waxes are a hard, white crystalline material derived from petroleum. They are refined by means of a carefully controlled selective solvent process into five difierent melting point grades, each having exceptional gloss and resistance to blocking. Parafiin waxes are predominately composed of normal, straight chain hydrocarbons. They vary from 18 to 40 carbon atoms and their chain length (i.e., molecular weight) determines their average melting point. Resistance to most acids and alkalis is very good. Illustrative of these waxes are the fully refined waxes: /127 AMP, 133/ 135 AMP, 138/140 AMP, 143/145 AMP and AMP, available from the Mobil Oil Corporation as reported in their technical bulletin RGM-085-011.

A further example of waxes are the microcrystalline waxes as illustrated by the Mobilwax 2300 series as reported in the Mobil Oil Corporation technical bulletin RGM 1-85-001.

Microcrystalline waxes consist of a matrix of extremely small crystals. They are sometimes referred to as amorphous wax-reflecting an early error based on the difliculty of identifying the presence of microscopic crystals. Their molecular structure consists of a complex mixture of hydrocarbons including normal paraflins, branched paraffins, monocyclic mompounds and polycyclic com pounds. The optimum ratio of each type of structure is controlled during the refining process to impart desired properties such as adhesive strength, cohesive strength, low temperature flexibility, and resistance to softening at elevated temperatures. Also included are mineral oils;

Esters, such as esters of organic alcohols and polybasic acids;

Resins and polymers, such as aromatic hydrocarbon resins and liquid elastomers (e.g., polyisobutylene and polybutene) Oils, pitch and resins obtained from pine trees and coal tar.

Natural fats and oils (vegetable oils, blown oils, fatty acids).

Coumarone indene resins (aromatic and aliphatic hydrocarbon resins which are derived from coal and petroleum oils) [Resins in Rubber, Gardner L. Brown, Pennsylvania Industrial Chemical Corp. (1969), p. 104].

As representative members of the petroleum oils one may specifically point to paraifinic petroleum oils such as Cyclolube 2310 (Golden Bear Oil Co.), naphthenic oils such as Shellflex 371 (Shell Chemical Company) and Cyclolube 138 (Golden Bear Oil Company) and aromatic oils such as Bearfiex LPO (Golden Bear Oil Company) and Califlux 550 (Golden Bear Oil Company). The esters are exemplified by butyl oleate, dibutylphthalate, and tricresyl phosphate, dioctyl sebacate, trioctyl phosphate and triethylene glycol caprylate. Illustrative of the resins and polymers are Kenflex N (see Kenflex for Neoprene, a technical bulletin available from Kenrich Corp., Maspeth, N.Y.; Kenflex N is a synthetic polymer of aromatic hydrocarbons which exists as an oily molecular weight (Staudinger) of 10,000-11,700), A-C polyethylene and copolymers available from Allied Chemical and reported in their technical data bulletin A-C Polyethylene (see below), and the Flosbrenes Fluid SBR polymers which are liquid or fluid copolymers of styrene and butadiene containing approximately bound styrene. Of particular interest in this class is Flosbrene 25 MV which has a molecular weight of approximately 5,000 and a viscosity in poises of 4,500 (77 F.) and 550 (113 F.) [The Flosbrenes Fluid SBR Polymers, A. G. Susie and F. J. Sackfield, American Synthetic Rubber Corp.]. Examples of coumarone indene resins which may be employed in the practice of the invention include the Picco resins which are a family of petroleum derived polyindene or coumarone indene type resins. Of particular interest is Pico 61001 /z and Piccotex 100 (alphamethylstyrene vinyl-toluene copolymer) (molar ratio of l-alpharnethylstyrene to 3-vinyltoluene) [Resins in Rubber, supra, pp. 72-75, 86 and Product Data Sheet-079, Pennsylvania Chemical Corp. p. 6]. Illustrative of vegetable oils which may be employed in the compounding of chloroprene polymers are linseed oil, rapeseed oil and safiiower oil.

The polybutenes are a series of synthetic hydrocarbon polymers obtained by catalytic polymerization of normal and branched chained butenes. They are pale colored liquids of moderate to high viscosity and tackiness. Representative of the class of polybutenes useful in the practice of the invention are the Oronite polybutenes [New Improved Oronite Polybutenes (1963), California Chemical Corp.]. Of particular interest is Polybutene No. 128.

Test method No. 6 No. 8 No. 16 No. 18 No. 20 No. 24 No. 32X No. 32 No. 122 No. 123

Physical Properties:

Condition Visual Clear, bright and free from sediment or suspended matter. Color, Gardner ASTM D4544 1 1 1 1 1 1 1 1 1 Specific gravity at 60I60 F-- ASTM D-287 0. 846 0. 862 0. 880 0.888 0. 891 0. 898 0. 905 0. 908 0. 915 0. 917 Numb er average molecular M-180-6 330 440 640 730 800 950 1, 260 1, 400 2, 500 2, 700

vgeight Mechrolab Osmome er. Mpleizular weight dispersion SM-180-6 1. 0 1. 5 1. 6 1. 8 2. 3

n ex. Viscosity at 100 F., SSU--- ASTM D-445 dz D-446 134 560 5, 700 9, 500 16, 500 40, 000 104, 000 123, 000 715, 000 890, 000 Viscosity at 210 F., SSU--- ASIIM D-445 dz D-446 41 63 250 350 550 1, 050 460 990 15, 800 19, 500 Viscosity index ASTM D-567 66 87 90 103 105 112 116 118 122 122 Flash point, F ASTM D-92 270 280 335 335 370 400 485 435 500 510 Fire point, F ASIM D-92 295 320 390 415 430 470 560 520 605 615 Pour point, F ASTM D-97 60 -10 +5 +10 +20 Loss on heating, percent (5 ASTM D-6 7. 6 1. 0 0. 3 0. 4 0. 1

hours at 325 F. Coelficient of thermal ex- SM1523 0. 00079 0 00078 0 00074 0. 00072 0. 00072 0. 00070 0. 00067 0. 00066 0 00063 0 00062 pension per C. (15 0- 100 0.). Chemical properties:

Bromine number, g./100. g SM-20-28 44 37 26 24 22 18 14 18 8 7 Neutrglization value, mg. ASTM D-664 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01

g. Organifitehloride: as chlorine, SM20512 0. 007 0. 004 0. 003 0. 003 0. 003 0. 003 0. 003 0. 003 0. 002 0. 002

weig percen Inforganic chlorides and sul- ASTM D-878 None None None None None None None None None None ates. Total sulfur, percent ASTM 13-1552 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 0. 01 Carbon residue, percent..-" ASTM D-189 None None None None None None None None None None Water content, p.p.m ASTM D4533 40 40 40 40 40 40 4O 40 40 liquid; specific gravity 60/60 F. of 1.01; melting point: 35 F.; flash point COC: 400 F.; yellow to light brown color), BRO-22 (see Barrett Standard Industrial Chemicals, 1955, published by the Barrett Division of Allied Chemical Corp., New York 'City; BRC-22 is a solid coaltar hydrocarbon which does not absorb sulfur; has a softening point of 205 to 220 F.; specific gravity of 1.26 to 1.35 and is 25% to 35% insoluble in CS Para-Flux (see Materials and Compounding Ingredients for Rubber, 1968, p. 184, published by Rubber World, New York City; Para-flux is a polymerized saturated petroleum hydrocarbon available from C. P. Hall; specific gravity, 0.98; black liquid; viscosity (140 F. Saybolt Furol), 250- 350 SUS: flash point (COC) 400 F.), Vistanex LM-MH (a non-staining polyisobutylene with a viscosity average As indicated above, mixtures of various plasticizers may be employed in the practice of the invention in addition to a single member. It has been found that desirable results are obtained when mixtures are employed, particularly when one of the members of the plasticizer mixture is either a liquid elastomer such as polyisobutylene, polybutene or the Flosbrenes or a coumarone indene resin such as Picco 6100-1-1/2 or Piccotex 100. The addition of the above plasticizers to the MgO dispersions improves the mixing and extrusion characteristics of the dispersion without affecting the dispersion performance in neoprene. When the liquid elastomers and coumarone indene resins are employed in combination with other plasticizers, they may be used at .4-20 parts by weight per hundred parts by weight of MgO.

The properties of typical petroleum oils which are employed as plasticizers are as follows:

8 PICCOTEX 100 Softening point, ball-and-ring C 100 SHELLFLEX 371 Color, Gardner scale (maximum) 1 Viscosity: Specific gravity 1.04 SSU/ 100 F. 420 Pounds per gallon, solid resin 8.67 SSU/ 210 F. 53.1 Gardner viscosity, in toluene at 25 C. Gravity, API 26.1 Acid number Less than 1 Specific gravity/ 60 F 0.8978 Saponification number Less than 1 Pounds/gallon 7.476 Bromine number (electrometric) Less thanl C A Ash percent Less than 0.1 Flash P P-' F 420 Refractive index at 25 C 1,583 Pour P 0 F- Ozone number o x if 111281225 Egg f Flash polnt, F 505 P Fire point, F 570 Dlstlllatlon, F.:

I P 7 Q at 70% solids. 5% 745 10% 757 PICCO 6100-1-1/2 50% 810 90% 5 Petroleum hydrocarbon resm (produced by the homo- Aniline Point, O 209 and copolymerization of dienes and olefins of the ali- UV absorptivity 260 my 0.9 pha ic, alicyclic, and monobenzenoid arylalkene types Viscosity-gravity constant 0.840 from distillates of cracked petroleum stocks) Refractive index/20 C 1.4890 Refractivity intercept 1.0423 Color, 6031 a 1 /2 Molecular analysis, clay-gel, percent w.: Melting P01 0 d g- C 100 Asphaltenes 0 Specific gravity 1.06 Polar compounds 0.3 Bromine No. (elec.) 10.3 Aromatlcs 15.5 Iodine No. (corrected) 16.4 saturates Refractive index, 25 C. 1 60 Carbon atom analysis, percent: (300 fl h point a F 480 g i f g atoms Acid number, max "1 ap t car on atoms N Saponification No., max. 1 Parafiimc carbon atoms, C 54 u ber e te di g on type 4 1 Ring and method Cyclolube Califiux Bearfiex o LPO 13s 4053 2310 Specific gravity F.. 1. 0217 0. 9679 0. 9573 0. 9053 0.9236 API gravity 7. 0 14. 7 16. 3 24. s 21. 7 color, ASTM D-1500.. D8. 0 2. 0 5 3. 0 3. 0 Viscosity, SUS at 313,000 2,500 539 1430 Viscosity, SUS at 210 475 38.1 86.3 56. 6 78. 9 Pour point, F 90 35 15 20 10 Flash point, COG, F.- 465 310 425 400 435 Fire point, 000, F-- 615 370 470 455 500 Aniline point, F 59. 0 158 204.1 195. 4 Mixed aniline point, F. 95. 8 Average molecular weight 435 255 411 436 410 Refractive index 20 0---- 1. 5843 1. 5422 1. 5294 1. 4936 1. 5043 Molecular analysis, ASTM D-2006 (Rostler) Asphaltenes None N one None None None Nitrogen bases... 31 2 10 1 Firsts da 5.. 22 17 14 4 9 Second acidafiins- 38 63 37 26 33 Paraffins 9 18 39 69 56 Gel aromatic- 91 82 61 31 44 Molecular analysl ASTM D 007 (Ola Asphalteues------ None None None None None Polar compounds 28 3 10 1 2 Aromatics- 63 77 50 26 40 saturates 9 20 40 73 58 Neutratiztion number.--- 0.04 0.03 0.04 0. 04 0.03 Viscosity index 1146 104 -56 43 18 Viscosity-gravity constant-- 0. 9667 0. 9520 0. 9020 0. 8426 0.8653 Rfrfictive intercept l. 0748 1. 0548 1. 0526 1. 0444 1. 0463 11 Z 54 38 23 6 10 7 34 37 40 43 39 28 40 54 47 Lbs wt./gal- The properties of typical mineral oils that are well known as plasticizers are as follows:

Kinematic Specific Saybolt viscosity ASIM pour pt. gravity viscosity (centistokes) Engler viscosity (max.). Flash pt. at C. at 37.8 0. at 37.8 0. 000 Grade No. or 60 F. or 100 C. or 100 F. 20 C. 50 0. C. F. (min) F.

350 USP .880/. 895 345/355 74/77 32.0 5.6 --23 -10 430 85 NF .845/. 860 80/90 15/18 5.0 2.0 7 +20 370 Softening point Hardness,

Viscosity- (ASTM E-28) loc. cps. 284 F. Percent (ASTM (ASTM (140 0.) vinyl F. C. D5) D-1505) (Brookfield) acetate Non-emulsifiable grades:

A-C polyethylenes:

Emulslfiable grades: Acid No A-C polyethylenes:

656 205 96 12 0. 92 120 15 629 and 629A- 219 104 5. 5 0.93 200 .15 655 225 107 2. 5 0. 93 210 15 680.. 230 110 1. 5 0. 94 250 16 392 280 138 0. 5 0. 99 9, 000 28 11-0 copolymer (organic acid type): 540 226 108 2. 0 0. 93 500 40 The surface active agents contemplated within the scope of this invention are either nonionic or ionic or mixtures thereof. As illustrative of classes of well known materials one may refer to the following:

Nonionic agents Sorbitan fatty acid esters,

Polyoxyethylene sorbitan fatty acid esters,

Polyoxyethylene sorbitol esters,

Polyoxyethylene acids,

Fatty alcohols,

Polyethylene glycols,

Nonylphenoxypoly (ethyleneoxy) ethanols,

Fatty acid esters of glycerol, ethylene glycol, polyethylene glycol, propylene, glycol,

Tetra esters of pentaerythritol and fatty acids.

Ionic agents Alkyl aryl sulfonates (e.g., dodecylbenzene sulfonate such as Atlas G-3300) Metallic soaps Representative examples of metallic soaps or fatty acid esters of metals that fall within the scope of the present invention are the stearates, oleates, palmitates and octoates of Ca, A1, Mg, and Fe. Other metals which may be utilized are Zn, Cd, Ba, Pb, Na, K, Li and Ni. Preferred examples of the metallic soaps are Mg stearate, Ca stearate, Al stearate, Fe distearate and Fe tristerate.

It should be noted that the choice of a specific surface active agent is not critical to the practice of the invention, as long as it be either nonionic or ionic and does not interfere with the neoprene vulcanization. Representative surface active agents include the following:

NONIONIC A GENTS Compound name Class Span 40, sorbitan monopahnitate... Sorbitan fatty acid ester. Span 80, sorbitan monooleate Do. Span 85, sorbitan trioleate Tween 20, Polyoxyethylene (20)--.- Tween 40, polyoxyethylene (20).. Sorb tan monopalmitate. Tween 60, polyoxyethylene (20).- Sorb tan rnonostearate. Tween 80, polyoxyethylene (20) Sorbitan monooleate. Renex 20, polyoxyethylene esters of Polyoxyethylene acids.

mixed fatty and resin acids.

D o. Sorbitan monolaureate.

1 Polyoxyethylene sorbitan fatty acid esters.

For further embodiments of nonionic and ionic agents that may be employed in the practice of this invention, attention is invited to publications such as General Characteristics of Atlas Surfactants (1963) and Detergents and 'Emulsifiers 1969 Annual, edited by John W. McCutcheon; the nonionic and ionic agents disclosed therein being incorporated by reference.

Representative examples of combinations of surface active agents include the following (the preferred ratio of the ingredients is indicated in parenthesis):

Span /Tween 60 (50/ 50) Span 80/Tween 80 (60/40) Span 80/T ween 80/ ethylene glycol monostearate (25/ Span 80/Tween 80/ glycerol monostearate (40/30/30) Span 80/Tween 80/epolene E-14 (20/15/65) Span SO/Tween 80/ Ca stearate (40/30/30) Span 80/Tween 80/carbowax 4000 (40/ 30/30) Span 80/ Ca stearate (60/40) Span 80/Al stearate (60/40) Igepal CO-43 0/ Ca stearate (67/33) Igepal CO-430/Al stearate (67/33) Although the precise reasoning for the highly improved results achieved by the dispersions of this invention containing a synergistic mixture of MgO and pentaerythritol or esters thereof is not entirely understood, it is thought that the beneficial effects may be due to pentaerythritol or its esters, in the presence of MgO, having a stabilizing effect on the polymer.

The pentaerythritol containing MgO dispersions of the invention may be prepared employing procedures well known in the art. An eflective method involves dispersing the MgO and pentaerythritol in the dispersing medium by vigorous mixing. High shear mixing is desirable. The dispersion can be made at room temperature, but elevated temperatures (80-120 C.) are preferred. It may be noted that particle size reduction of the MgO (prior to, after, or during making the dispersion) improves the dispersion performance.

All dispersions used in the following examples were prepared in a double arm sigma blade mixer. The mixer has a working capacity of 0.7 gal, and is jacketed for steam heating. The dispersions were prepared by adding all ingredients including pentaerythritol but except MgO, and mixing with heating until a temperature of -105 C. was reached, then the MgO was added and mixing was continued at 100105 C. until complete wetting of the MgO and the pentaerythritol by the dispersing medium.

The neoprene compounding was done on a two-roll laboratory rubber mill. The rubber mill has a front roll and a back roll, each six inches in diameter and thirteen inches in length. The front roll is operated at 24 revolutions per minute, and the back roll is operated at 33.6 revolutions per minute. A 7.5 horsepower motor is used to operate the mill. The composition of the neoprene rubber used in the following examples is as follows:

Neoprene rubber Parts Neoprene GNA 100 Stearic acid 0.5

MgO powder or dispersion (with or without pentaerythritol) 4 The rubber is banded on the front roll of the laboratory mill, and the mill is operated until the band is smooth and free of holes. In succession, stearic acid, MgO (powder or dispersion), carbon black, Neozone A and ZnO are added. Each ingredient is added evenly across the rolls and at a uniform rate and is assimilated into the mix before the next ingredient is added. After mixing, the batch is removed from the mill, weighed, and again placed into the mill. The rolls are set at a distance of 0.030 inch from each other. The stock is passed through the mill six times. During the milling, water having a temperature of 68 F. is passed through the rolls. The stock is then sheeted from the mill.

Mooney scorch performance was determined with a Monsanto Mooney rheometer at 127 C. using a small rotor according to ASTM Test Method Dl646-63.

The Neoprene Grade MgO used in the following examples is Maglite D No. 3231, a light calcined, high surface activity, magnesium oxide produced by Merck & Co., Inc. It has the following typical properties:

Chemical analysis Typical, percent Magnesium oxide, MgO 93.10 Ignition loss 4.86 Carbon dioxide, CO 0.46 Combined water, H O 4.40 Calcium oxide, CaO 0.79 Silicon dioxide, SiO 0.27 Chloride, Cl 0.17 Sulfate, S 0.68 Iron oxide, Fe O 0.03 Aluminum oxide, A1 0 0.10 Manganese, Mn 0.0017 Copper, Cu 0.0002 Acid insoluble 0.05

Physical analysis Typical Appearance (1) Refractive index 1.64 Specific gravity 3.32 Weight per gallon .lb./gal 2.8 Bulk (loose) pcf 21 Screen analysis:

Through 100 mesh percent 100 Through 200 mesh do 100 Through 325 mesh do 99.5

1 Clean, white, odorless powder.

12 Primary Particle size, as determined by an electron microscope:

Average distribution microns 0.086 0-0.05 micron percent 20.9 0.05-0.10 micron do 48.8 0.100.15 micron do 20.2 0.15-0.20 micron do 7.1 0.20-0.25 micron do 3.0

Surface area ..m. /gm. 185 Iodine number 135 The dispersions were compounded in a neoprene rubber formulation indicated previously using a laboratory mill; they were used at 4 phr. (parts per of rubber). For comparison, Maglite D powder was similarly compounded, and used at 4 phr.

The performance of the dispersions and powder additions to the neoprene compound was judged from Mooney scorch times. The 2 is the time required for the Mooney viscosity to increase 10 units above the minimum. Desirably, the r times for original Mooney Scorch should be relatively long (similar to what results from the use of Maglite D powder at 4 phr.). Next, the unvulcanized compounds were aged during 6 days at 50 C., after which the Mooney viscosity r time was determined. Desirably, the t time should change little during bin aging. If the t times of the original or the bin aged compounds are short, then the rubber processor does not have sufficient time to process and vulcanize his compounds. This results in scrap. Relatively high t times reduce losses due to scrap and allow less critical conditions for processing and storage of the unvulcanized neoprene compounds.

EXAMPLE I In this example the performance of a MgO dispersion with pentaerythritol (reagent grade) is compared to a similar dispersion without this synergistic additive, using mineral oil as the dispersing medium. The dispersions were used at 4 phr. in neoprene.

Original and bin age Mooney scorch protection tie time Dispersion composition (weight percent) (minutes) After 6 Penta- Mineral days at Maglite D erythritol oil Original 50 C.

50 s 50 34 18 40 1O 5O 44 28 The results clearly show the beneficial synergistic effect produced by pentaerythritol.

EXAMPLE II Dispersion composition (weight percent) Original and bin age Mooney scorch protection no time (minutes) 13 The example shows that the dispersions of the invention give better performance than either powder or a dispersion without entaerythritol.

EXAMPLE III Similarly a dispersion can be prepared and evaluated using the following composition:

Weight percent MgO 50 Pentaerythritol Surface active agent 47.5

EXAMPLE IV 14 Dispersion composition:

Percent Maglite D 55.6 Naphthenic petroleum oil 31.1 Sorbitan mono-oleate 2.7 Calcium stearate 1.8 Pentaerythritol 4.4 Pentaerythritol mono-ricinoleate 4.4

Performance in neoprene comparison:

Ori al and bin age ooney scorch protection tm time (minutes) After 6 days at MgO Original 50 C.

Dispersion 46 43 Maglite D powder 38 29 The above example is further evidence of the improvement in performance employing the dispersions of the invention.

EXAMPLE VII g figggg g gig Illustrative of the dispersions that may be employed in protection n time the practice of the invention are the following: Dispersion composition (weight percent) (minutes) Percent Pentae- MgO 54.0 $2 12} 55%;; Naphthenic process oil 36-0 MagliteD inoleate on Original 50C. Picco 6100-1 1/2 3.0 50 3 45 33 30 Pentaerythritol mono-ricinoleate 3.0 43 37 Sorbitan mono-oleate 2.5 $3 32 Calcium stearate 1.5 MgO 52.0 35 Naphthenic process oil 43.0 The example Shows that the use of entaerythritol P y i l mono-stearate mono-ricinoleate enhances the performance of MgO dis- Pentaerythntol tetra-Swarm persions to give a performance equal to or better than the Mg() 50.0 p Naphthenic process oil 45.0 EXA V Pentaerythritol tri-stearate 5.0 MgO is dispersed in a dispersing medium consisting of i g a naphthenic petroleum oil (Shellflex 371 a technical i 3 1% grade of pentaerythritol mono-ricinoleate and one or th l 1 f the following sorbitan mono-oleate (surface en aery n 0 1-0 eate Nonylphenoxypoly (ethyleneoxy) ethanol 4.0 active agent), pentaerythritol tetra-stearate (surface ac- Mgo 56.0 tive agent) and pentaerythritol. Butyloleate 3 5 The dispersions are used in neoprene at a level of 4 phr. polybutene 23 (oronite) 2,5 and the performance is compared with Maglite D powder Glycerol monostearate 3.0 at 4 phr. Pentaerythritol di-laurate 3.5

Original and bin age Composition (welght percent) Mooney scorch protection i time (minutes) Penta- Pentaerythritol Sorbitan erythritol After 6 monomonotetra- Pentadays at Maglite D ricinoleate oleate Stearate erythritol Oil Original 50 C.

5 5 40 45 3s 5 5 4o 44 as 5 5 40 43 39 50 5 5 5 5 35 45 39 100 (Maglite D powde 38 34 The above example demonstrates the use of pentaerythritol solely or in combination with esters of pentaerythritol to enhance the performance of MgO dispersions. Mgo Dibutyl phthalate 30.0 EXAMPLE VI Vistanex LM-MH 4.0 In this example, the performance of an MgO disper- Nonylphemfl pohiglycol ether (Tergltol NPX) i of hi invention using entaerythritol mono-ricin- Pentaerythntol dl'acetate oleate, is compared with MgO powder. In previous ex- Mgo 52 0 amples, the neoprene test compound was mixed on an open rubber mill. In this example, the neoprene test com- Paraffimc petroleum on (cyclolube 2310) pound was mixed in an internal mixer (Banbury, type Al'stearate 00). Maglite D powder and dispersion are each used at 4 yl aryl sulfonate (Atlas G-3300) 6.0 phr. in neoprene. Pentaerythritol mono-acrylate 7.0

Percent MgO 52.0 Shellfiex 371 31.5 Fully refined wax 138/140 (Mobil) 2.5 Microcrystalline wax Mobil wax 2305 BR 2.5 Polyethylene glycol (Carbowax 4000) 5.0 Pentaerythritol tri-sorbate 7.5 MgO 51.0 Linseed oil 33.5 Polyethylene AC 617 5.0 Emulphor VN-430 6.0 Pentaerythritol-monobenzoate 4.5 MgO 75.0 Shellflex 371 16.0 Picco 6100-1 1/2 2.0 Pentaerythritol mono-ricinoleate 4.0 Sorbitan mono-oleate 2.5 Calcium stearate 1.5

Preparation of stick or bar form of pentaerythritol containing MgO dispersion After the dispersion is prepared by high shear mixing, the hot dispersion is extruded through a hot extruder. The extruded stick is then cut into the desired lengths, and cooled to room temperature.

Preparation of pellet form of pentaerythritol containing MgO dispersion Pellets are prepared by adding the hot dispersing medium to the powder while it is being mixed slowly at about 100 C. Just enough dispersing medium is added to make the particles coalesce.

When certain representative embodiments and details have been shown for the purpose of illustrating the invention it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

What is claimed is:

1. A composition for use in the compounding and processing of chloroprene polymers comprising pentaerythritol or the mono-, diand tri-esters thereof wherein the acid residue is derived from an aliphatic acid moiety of from about 1 to 18 carbon atoms, benzoic acid or phthalic acid or mixtures thereof and a dispersion of MgO wherein there is present from about 2 to about 100 parts by weight of pentaerythritol or the esters thereof per hundred parts by weight of MgO and from about 5 to 200 parts by weight of dispersing medium per hundred parts by weight of MgO.

2. The composition according to claim 1 wherein the dispersing medium comprises at least one rubber plasticizer; at least one ionic or non-ionic surface active agent or mixtures thereof or a mixture of at least one rubber plasticizer with at least one ionic or non-ionic surface active agent or mixtures thereof and the pentaerythritol material is selected from the group consisting of pentaerythritol and the mono-, diand tri-esters thereof wherein the acid residue is derived from an acid selected from the group consisting of formic, acetic, acrylic, glycoxylic, acetoacetic, maleic, adipic, methacrylic, heptanoic, pivalic, nonanoic, azelaic, glycolic, benzoic and phthalic or mixtures thereof.

3. The composition according to claim 2 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monostearate, pentaerythritol disterate, pentaerythritol tol tristearate, pentaerythritol monooleate, pentaerythtol tristearate, pentaerythriol monooleae, penaerythritol monoricinoleate, pentaerythritol diricinoleate, pentaerythritol triricinoleate, pentaerythritol monopalmitate, pentaerythritol dipalmitate, pentaerythritol tripalimitate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate, pentaerythritol monolinoleate, pentaerythritol dilinoleate and pentaerythritol trilinoleate,

4. The composition according to claim 3 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monosterate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol monooleate, pentaerythritol dioleate and pentaerythritol monoricinoleate.

5. The composition according to claim 4 wherein the dispersing medium comprises at least one rubber plasticizer.

6. The composition according to claim 5 wherein the rubber plasticizer is a petroleum oil.

7. The composition according to claim 6 wherein the rubber plasticizer is a petroleum oil and a coumarone indene resin.

8. The composition according to claim 4 wherein the dispersing medium is a mixture of at least one rubber plasticizer and at least one ionic or non-ionic surface active agent or mixtures thereof.

9. The composition according to claim 8 wherein the nonionic surface active agent is selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, fatty alcohols, polyethylene glycols, nonylphenoxypoly (ethyleneoxy) ethanols, fatty acid esters of glycerol, ethylene glycol, polyethylene glycol or propylene glycol, and tetra esters of pentaerythritol and fatty acids and the ionic surface active agent is an alkyl aryl sulfonate or a metallic soap and the rubber plasticizer is a petroleum oil or a petroleum oil and a coumarone indene resin.

10. The composition according to claim 9 wherein the nonionic surface active agent is a sorbitan fatty acid ester and the ionic surface active agent is a metallic soap and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin.

11. The composition according to claim 10 wherein the surface active agent is a mixture of sorbitan monooleate and calcium stearate.

12. The composition according to claim 9 wherein the surface active agent is nonylphenoxypoly(ethyleneoxy) ethanol and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin 13. The composition of claim 11 wherein the pentaerythritol material is pentaerythritol.

14. The composition of claim 12 wherein the pentaerythritol material is pentaerythritol.

15. A process of producing a vulcanizable chloroprene polymer which comprises the addition of pentaerythritol or the mono-, diand tri-esters thereof wherein the acid residue is derived from an aliphatic acid moiety of from about 1 to 18 carbon atoms, benzoic acid or phthalic acid or mixtures thereof and a dispersion of MgO to a composition comprising chloroprene polymer wherein there is present from about 2 to about parts by weight of pentaerythritol per hundred parts by weight of MgO, from about 5 to 200 parts by weight of dispersing medium per hundred parts by weight of MgO wherein the MgO, pentaerythritol or the esters thereof and dispersing medium is present in the amount of from about 2 to about 16 parts by weight per hundred parts by weight of polymer.

16. The process according to claim 15 wherein the dispersing medium comprises at least one rubber plasticizer; at least one ionic or non-ionic surface active agent or mixtures thereof or a mixture of at least one rubber plasticizer with at least one ionic or non-ionic surface active agent or mixtures thereof and the pentaerythritol material is selected from the group consisting of pentaerythritol and the mono-, diand tri-esters thereof wherein the acid residue is derived from an acid selected from the group consisting of formic, acetic, acrylic, glycoxylic, acetoacetic, maleic, adipic, methacrylic, heptanoic, pivalic, nonanoic, azelaic, glycolic, benzoic and phthalic or mixtures thereof.

17. The process according to claim 16 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol monoricinoleate, pentaerythritol diricinoleate, pentaerythritol triricinoleate, pentaerythritol monopalmitate, pentaerythritol dipalmitate, pentaerythritol tripalmitate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate, pentaerythritol monolinoleate, pentaerythritol dilinoleate and pentaerythritol trilinoleate.

18. The process according to claim 17 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol monooleate, pentaerythritol dioleate and pentaerythritol monoricinoleate.

19. The process according to claim 18 wherein the dispersing medium comprises at least one rubber plasticizer.

20. The process according to claim 19 wherein the rubber plasticizer is a petroleum oil.

21. The process according to claim 20 wherein the rubber plasticizer is a petroleum oil and a coumarone indene resin.

22. The process according to claim 18 wherein the dispersing medium is a mixture of at least one rubber plasticizer and at least one ionic or non-ionic surface active agent or mixtures thereof.

23. The process according to claim 22 wherein the nonionic surface active agent is selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, fatty alcohols, polyethylene glycols, nonylphenoxypoly (ethyleneoxy) ethanols, fatty acid esters of glycerol, ethylene glycol, polyethylene glycol or propylene glycol, and tetra esters of pentaerythritol and fatty acids and the ionic surface active agent is an alkyl aryl sulfonate sulfonate or a metallic soap and the rubber plasticizer is a petroleum oil or a petroleum oil and a coumarone indene resin.

24. The process according to claim 23 wherein the nonionic surface active agent is a sorbitan fatty acid ester and the ionic surface active agent is a metallic soap and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin.

25. The process according to claim 24 wherein the surface active agent is a mixture of sorbitan monoleate and calcium stearate.

26. The process according to claim 23 wherein the sur face active agent is nonylphenoxypoly (ethyleneoxy) ethanol and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin.

27. The process of claim 25 wherein the pentaerythritol material is pentaerythritol.

28. The process of claim 26 wherein the pentaerythritol material is pentaerythritol.

29. A bar or pellet for use in the compounding and processing of chloroprene polymers comprising pentaerythritol or the mono-, diand tri-esters thereof wherein the acid residue is derived from an aliphatic acid moiety of from about 1 to 18 carbon atoms, benzoic acid or phthalic acid or mixtures thereof and a dispersion of MgO wherein there is present from about 2 to about 100 parts by weight of pentaerythritol or the esters thereof per hundred parts by weight of MgO, from about to 200 parts by weight of dispersing medium per hundred parts by weight of MgO.

30. The bar or pellet according to claim 29 wherein the dispersing medium comprises at least one rubber plasticizer; at least one ionic or non-ionic surface active agent or mixtures thereof or a mixture of at least one rubber plasticizer with at least one ionic 0r non-ionic surface active agent or mixtures thereof and the pentaerythritol material is selected from the group consisting of pentaerythritol and the mono-, diand tri-esters thereof wherein the acid residue is derived from an acid selected from the group consisting of formic, acetic, acrylic, glycoxylic, acetoacetic, maleic, adipic, methacrylic, heptanoic, pivalic, nonanoic, azelaic, glycolic, benzoic and phthalic or mixtures thereof.

31. The bar or pellet according to claim 30 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol monoricinoleate, pentaerythritol diricinoleate, pentaerythritol triricinoleate, pentaerythritol monopalmitate, pentaerythritol dipalmitate, pentaerythritol tripalmitate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate, pentaerythritol monolinoleate, pentaerythritol dilinoleate and pentaerythritol trilinoleate.

32. The bar or pellet according to claim 31 wherein the pentaerythritol material is at least one member selected from the group consisting of pentaerythritol, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearae, pentaerythritol monooleate, pentaerythritol dioleate and pentaerythritol monoricinoleate.

33. The bar or pellet according to claim 32 wherein the dispersing medium comprises at least one rubber plasticizer.

34. The bar or pellet according to claim 33 wherein the rubber plasticizer is a petroleum oil.

35. The bar or pellet according to claim 34 wherein the rubber plasticizer is a petroleum oil and a coumarone indene resin.

36. The bar or pellet according to claim 32 wherein the dispersing medium is a mixture of at least one rubber plasticizer and at least one ionic or non-ionic surface active agent or mixtures thereof.

37. The bar or pellet according to claim 30 wherein the nonionic surface active agent is selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene orbitol esters, polyoxyethylene acids, fatty alcohols, polyethylene glycols, nonylphenoxypoly (ethyleneoxy) ethanols, fatty acid esters of glycerol, ethylene glycol, polyethylene glycol or propylene glycol, and tetra esters of pentaerythritol and fatty acids and the ionic surface active agent as an alkyl aryl sulfonate or a metallic soap and the rubber plasticizer is a petroleum oil or a petroleum oil and a coumarone indene resin.

38. The bar or pellet according to claim 37 wherein the nonionic surface active agent is a sorbitan fatty acid ester and the ionic surface active agent is a metallic soap and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin.

39. The bar or pellet according to claim 38 wherein the surface active agent is a mixture of sorbitan monooleate and calcium stearate.

40. The bar or pellet according to claim 37 wherein the surface active agent is nonylphenoxypoly (ethyleneoxy) ethanol and the rubber plasticizer is a naphthenic petroleum oil or a naphthenic petroleum oil and a coumarone indene resin.

41. The bar or pellet of claim 39 wherein the pentaerythritol material is pentaerythritol.

42. The bar or pellet of claim 40 wherein the pentaerythritol material is pentaerythritol.

References Cited UNITED STATES PATENTS 2,567,117 9/1951 Mochel 260-923 MAURICE I. WELSH, Primary Examiner US. Cl. X.R.

252-182, 188.3, 309; 260-23.7 H, 33.6 AQ, 92.3

UNTTED STATES TATE OFFICE CERTIFICATE OF ECTIUN Patent No. 3,810,856 Dated M g 974 InTentofls) Albert J. Dalhuisen and William H. Deis It is certified that error appears in the sheve ideutified patent and that said Letters Patent are hereby corrected as shown below:

Column 15, Claim 3, line 4 delete [disterate] and substitute therefor distearate Column 15, Claim 3, line 5 should read:

-- tristearate, pentaerythritol monooleate, pentaerythritol Column 15, Claim 3, line 6 should be deleted.

Column 16, Claim 4, line 2 delete [monosterate] and substitute therefor monostearate Column 35f Claim 3, line 9 delete {tripalimitate} and substitute therefor tripalmitate Column 1?, Claim 23, line 10 delete [sulfonate] the second, time it appears.

Column 1?, Claim 25, line 2 delete [monoleate] and substitute therefor monooleate Column 18, Claim 37, line 4 delete [orbitol] and substitute therefor sorbitol Column 18, Claim 37, line 9 delete {as} and substitute therefor is Column 18, Claim 32, line 5 delete [tristearae] and substitute therefor tristearate Signed and sealed this 15th day of October 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. (3. mRsTmLL DANN Arresting Officer Commissioner of UNITED STATES tATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,810,856 Dated 4 Inventor) Albert J. Dalhuisen and William H. Deis It is certified thet error e-ppeere in eheve idemtified patent and that said Letters Patent ere herety corrected es shown below:

Column 15, Claim 3, line 4 delete [disterete] and substitute therefor distearate Column 15, Claim 3, line 5 should read:

-- tristearate, pentaerythritol monooleate, pentaerythritol Column 15, Claim 3, line 6 should be deleted.

Column 16, Claim 4, line 2 delete [monosterate] and substitute therefor monostearate Column Claim 3, line 9 delete [tripalimitate] and substitute therefor tripalmitate Column 1?, Claim 23, line 10 delete [sulfonate] the second time it appears.

Column 1?, Claim 25, line 2 delete [monoleate] and substitute therefor monooleete Column 18, Claim 37, line 4 delete [orbitol] and substitute therefor sorbitol Column 18, Claim 37, line 9 delete {as} and substitute therefor is Column 18, Claim 32, line 5 delete itristearae] and substitute therefor tristearete Signed and sealed this 15th day of October 1974.

SEAL) Attest:

MCCOY M GIBSON JR. Cu MARSHALL DANN Attesting Officer Commissioner of Petttzmtze 

